BACTERICIDAL COMPOSITION

Abstract: The present invention provides a fungicidal composition characterized by containing as active ingredients (a) a compound represented by the formula I: (wherein Ar is a substituted or unsubstituted phenyl group, Y is an oxygen atom, an oxymethylene group or a methyleneoxy group, X is NR 1 R 2 or OR 3 , and R 1 , R 2 and R 3 , which may be the same or different, are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms), and (b) at least one compound selected from the group consisting of ethylenebis(dithiocarbamate) type fungicidal compounds, N-(3,5-dichlorophenyl)imide type fungicidal compounds, Chlorothalonil, phthalimide type fungicidal compounds, anilide type fungicidal compounds, Cymoxanil, Fosetyl, cyanopyrrole type fungicidal compounds, anilino type heterocyclic fungicidal compounds, benzimidazole type fungicidal compounds and their precursors, sulfur, copper compounds, and carbamate type fungicidal compounds for controlling fungi tolerant to benzimidazole type fungicides.

Description: TECHNICAL FIELD The present invention relates to a fungicidal composition mainly for agricultural and horticultural use. BACKGROUND ART Various agricultural and horticultural fungicides have been known, but there are a great variety of diseases to be controlled and it is difficult to specify the kind of the disease in practice and control the disease by choosing a fungicide suitable for the disease. In addition, it is necessary to cope with the appearance of fungi which have aquired tolerance to specific agents and the occurence of novel diseases due to the change of the mode of agriculture. For these reasons and the like, there is desired a fungicidal composition having a high activity and a wide antimicrobial spectrum. The present invention provides a fungicidal composition which has a high activity and a wide antimicrobial spectrum and is markedly effective also against diseases caused by plant pathogenic fungi which have aquired tolerance to certain fungicides. DISCLOSURE OF THE INVENTION In detail, the present invention provides a fungicidal composition characterized by containing as active ingredients synergistically effective amounts of (a) methyl α-methoxyimino-2-[(2-methylphenoxy)methyl]phenylacetate (b) at least one compound selected from ethylenebis(dithiocarbamate) type fungicidal compounds and N-(3,5-dichlorophenyl)imide type fungicidal compounds as set out below. The ethylenebis(dithiocarbamate) type fungicidal compound or compounds are selected from zinc salt (Zineb), manganese salt (Maneb), salt with zinc and manganese (Mancozeb). The N-(3,5-dichlorophenyl)imide type compound or compounds are selected from N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxyimide (Procymidone), 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (Vinclozolin) and 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide (Iprodione) which are fungicidal compounds having a partial structure represented by Compound (a) has been disclosed in, inter alia, EP 253 213 A1 and EP 254 426 A1, both of which documents mention various combination partners for the oximether compounds without specifying particular advantageous combinations. EP 524 496 A1 discloses synergistic combinations of compound (a) with Fenpropimorph, Tridemorph or Fenpropidin. EP 645 089 A1, published on 29.03.95, after the latest date of priority of the application, discloses synergistic mixtures of an amide analogue of (a) with ethylenebis(dithiocarbamates). Plant diseases that can be controlled by the composition of the present invention include blast (Pyricularia oryzae), Helminthosporium leaf spot (Cochliobolus miyabeanus) and sheath blight (Rhizoctonia solani) of rice; powdery mildew (Erysiphe graminis f. sp. hordei, f. sp. tritici), scab (Gibberella zeae), rust (Puccinia striiformis, P. graminis, P. recondita, P. hordei), snow blight (Typhula sp., Micronectriella nivalis), loose smut (Ustilago tritici, U. nuda), bunt (Tilletia caries), eye spot (Pseudocercosporella herpotrichoides), foot rot (Rhizoctonia cerealis), scald (Rhynchosporium secalis), leaf blight (Septoria tritici) and glume blotch (Leptosphaeria nodorum) of barley, wheat, oats and rye; melanose (Diaporthe citri), scab (Elsinoe fawcetti), penicillium rot (Penicillium digitatum, P. italicum) of citrus; blossom blight (Sclerotinia mali), canker (Valsa mali), powdery mildew (Podosphaera leucotricha), Alternaria leaf spot (Alternaria mali) and scab (Venturia inaequalis) of apple; scab (Venturia nashicola), black spot (Alternaria kikuchiana) and rust (Gymnosporangium haraeanum) of pear; brown rot (Sclerotinia cinerea), scab (Cladosporium carpophilum) and Phomopsis rot (Phomopsis sp.) of peach; downy mildew (Plasmopara viticola), Sphaceloma scab (Elsinoe ampelina), ripe rot (Glomerella cingulata), powdery mildew (Uncinula necator) and rust (Phakopora ampelopsidis) of grape; anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) of Japanese persimmon; cucumber downy mildew (Pseudoperonospora cubensis); anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea) and gummy stem blight (Mycosphaerella melonis) of melons and cucumbers; early blight (Alternaria solani), leaf mold (Cladosporium fulvum) and late blight (Phytophthora infestans) of tomato; brown spot (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) of eggplant; leaf spot (Alternaria brassicae) and white spot (Cercosporella brassicae) of vegetables of Cruciferae; onion rust (Puccinia allii); purple stain (Cercospora kikuchii), Sphaceloma scab (Elisinoe glycines) and pod and stem blight (Diaporthe phaseolorum var. sajae) of soybean; kidney bean anthracnose (Colletotrichum lindemthianum); leaf spot (Mycosphaerella personatum) and leaf spot (Cercospora arachidicola) of peanut; powdery mildew (Erysiphe pisi) and downy mildew (Peronospora pisi) of pea; downy mildew (Peronospora viciae) and Phytophthora rot (Phytophthora nicotianae) of broad bean; early blight (Alternaria solani) and late blight (Phytophthora infestans) of potato; powdery mildew (Sphaerotheca humuli) and Phytophthora rot (Phytophthora nicotianae) of strawberry; net blister blight (Exobasidium recticulatum) and white scab (Erysiphe leucospila) of tea plant; brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichum tabacum) and Phytophthora rot (Phytophthora parasitica) of tobacco; beet leaf spot (Cercospora beticola); black spot (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa) and Phytophthora rot (Phytophthora megasperma) of rose; leaf spot (Septoria chrysanthemella) and white rust (Puccinia horiana) of chrysanthemum; gray mold (Botrytis cinerea) and stem rot (Sclerotinia sclerotiorum) of fruit trees such as grape and citrus and various crops such as cucumber, tomato, beans and vegetables; and plant diseases caused by Pythium fungi (Pythium sp.). In the fungicidal composition of the present invention, although the mixing proportions of the compound (a) used as active ingredient and the other active ingredient(s) selected from the group of compounds (b) are not particularly limited, the mixing may be carried out so as to adjust the amount of the compound of the formula I mixed with each of the other active ingredient(s) as follows. Next, the weight of the at least one compound selected from the group (b) and mixed with 1 part by weight of the compound (a) is described below. The proportion of the ethylenebis(dithiocarbamate) compound(s) ranges usually from 0.01 to 100 parts by weight, preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per part by weight of the compound of the formula I. The mixing proportion of the N-(3,5-dichlorophenyl)imide type compound(s) is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight. The fungicidal composition of the present invention is applied usually after being formulated into an emulsifiable concentrate, wettable powder, suspension, granules, dust, dry flowable concentrate, aqueous soluble concentrate, oil formulation, smoking formulation, aerosol, microcapsules or the like, by mixing with a solid carrier, liquid carrier or gaseous carrier and optionally addition of adjuvants for formulation such as surfactants, fixing agents, dispersants, stabilizers, etc. The compounds as active ingredients are usually contained in such a formulation in a total amount of 0.1 to 99% by weight, preferably 0.2 to 90% by weight. The solid carrier includes, for example, fine powders or granules of clays (e.g. kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, attapulgite clay, bentonite and acid clay), talcs, other inorganic minerals (e.g. sericite, powdered quartz, powdered sulfur, activated carbon, calcium carbonate and hydrated silica), and salts for chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride). The liquid carrier includes, for example, water, alcohols (e.g. methanol and ethanol), ketones (e.g. acetone, methyl ethyl ketone and cyclohexanone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene and methylnaphthalene), aliphatic hydrocarbons (e.g. hexane and kerosene), esters (e.g. ethyl acetate and butyl acetate), nitriles (e.g. acetonitrile and isobutyronitrile), ethers (e.g. dioxane and diisopropyl ether), acid amides (e.g. dimethylformamide and dimethylacetamide), and halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene and carbon tetrachloride). The gaseous carrier includes butane gas, carbon dioxide, fluorocarbon gas, etc. The surfactants include alkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethers and their polyoxyethylenated products, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, etc. The fixing agents and dispersants include casein, gelatin, polysaccharides (e.g. starch, gum arabic, cellulose derivatives and alginic acid), lignin derivatives, bentonite, saccharides, synthetic watersoluble polymers [e.g. poly(vinyl alcohol)s, poly(vinylpyrrolidone)s and poly(acrylic acid)s], etc. The stabilizers include PAP (acidic isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids or their esters, etc. The above-mentioned formulations are applied to plants or soil as they are or after being diluted with water or the like. When applied to soil, they may be sprinkled on the soil surface or mixed with the soil. They may be applied also by any of various methods such as seed treatment, ULV, etc. When used as a seed-treating agent, the formulations are used by dressing of seeds, seed immersion or the like. In addition, the formulations may be used in combination with other fungicides, insecticides, acaricides, nematicides, herbicides, seed disinfectants, fertilizers, soil conditioners, etc. Although the applying dosage of the fungicidal composition of the present invention is varied depending on the kinds of the compounds used as active ingredients; their mixing proportions; weather conditions; type of formulation; application time, method and site; diseases to be controlled; a crop to be protected; and the like, it is usually 0.001 to 1000 g, preferably 0.1 to 100 g, per are. When the emulsifiable concentrate, wettable powder, suspension, soluble concentrate or the like is used after being diluted with water, the applying concentration thereof is 0.0001 to 1% by weight, preferably 0.001 to 0.5% by weight. The granules, dust and the like are used as they are without dilution. For seed treatment, the fungicidal composition is used in an amount of usually 0.001 to 50 g, preferably 0.01 to 10 g, (in terms of the sum of the compounds used as active ingredients) per kg of seeds. EXAMPLES The present invention is explained below in further detail with formulation examples and test examples, but the present invention is not limited to the following examples. In the following examples, parts and percents are all by weight unless otherwise specified. Formulation Example 1 Granules are obtained by thoroughly grinding and mixing 1 part of compound (a), 5 parts of an ethylenebis(dithiocarbamate) compound, 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 61 parts of kaolin clay, and thoroughly kneading the resulting mixture together with water, followed by granulation and drying. Formulation Example 2 Granules are obtained by thoroughly grinding and mixing 5 parts of compound (a), 5 parts of an ethylenebis(dithiocarbamate) compound, 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 57 parts of kaolin clay, and thorougly kneading the resulting mixture together with water, followed by granulation and drying. Formulation Example 3 A dust is obtained by thoroughly grinding and mixing 0.5 part of compound (a), 2.5 parts of an ethylenebis(dithiocarbamate) compound, 86 parts of kaolin clay and 11 parts of talc. Formulation Example 4 A suspension is obtained by mixing 5 parts of compound (a), 25 parts of an ethylenebis(dithiocarbamate) compound, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of carboxymethyl cellulose and 64 parts of water, followed by wet grinding to a particle size of 5 microns or less. Formulation Example 5 A wettable powder is obtained by thoroughly grinding and mixing 10 parts of compound (a), 50 parts of an ethylenebis(dithiocarbamate) compound, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 35 parts of synthetic hydrated silicon dioxide. Formulation Example 6 An emulsifiable concentrate is obtained by mixing 5 parts of compound (a), 25 parts of an ethylenebis(dithiocarbamate) compound, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 50 parts of xylene. Formulation Example 7 Granules are obtained by thoroughly grinding and mixing 1 part of compound (a), 5 parts of Procymidone, Vinclozolin or Iprodione, 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 61 parts of kaolin clay, and thoroughly kneading the resulting mixture together with water, followed by granulation and drying. Formulation Example 8 Granules are obtained by thoroughly grinding and mixing 5 parts of compound (a), 5 parts of Procymidone, Vinclozolin or Iprodione, 1 part of synthetic hydrated silicon dioxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 57 parts of kaolin clay, and thoroughly kneading the resulting mixture together with water, followed by granulation and drying. Formulation Example 9 A dust is obtained by thoroughly grinding and mixing 0.5 part of compound (a), 2.5 parts of Procymidone, Vinclozolin or Iprodione, 86 parts of kaolin clay and 11 parts of talc. Formulation Example 10 A suspension is obtained by mixing 5 parts of compound (a), 25 parts of Procymidone, Vinclozolin or Iprodione, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of carboxymethyl cellulose and 64 parts of water, followed by wet grinding to a particle size of 5 microns or less. Formulation Example 11 A wettable powder is obtained by thoroughly grinding and mixing 10 parts of compound (a), 50 parts of Procymidone, Vinclozolin or Iprodione, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 35 parts of synthetic hydrated silicon dioxide. Formulation Example 12 An emulsifiable concentrate is obtained by mixing 5 parts of compound (a), 25 parts of Procymidone, Vinclozolin or Iprodione, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 50 parts of xylene. Test Example 1 A tomato plant (cultivar: Ponterosa) was planted in each pot and was sprayed with a sufficient volume of a dilution with a predetermined concentration of a wettable powder obtained according to Formulation Example 5, after the plant put out a third leaf. After air-drying of the liquid chemical, the surfaces of the leaves were inoculated with a suspension of spores (5 x 104 spores/ml) of tomato late blight fungus (Phytophthora infestans) by spraying. The plant was grown at 24°C for 1 week, after which the infection rate (%) was investigated. The results are shown in Table 1. Agent tested Amount of agent applied (ppm) Infection rate (%) Compound (a) 10 25 Mancozeb 50 25 Compound (a) + Mancozeb 10 + 50 0 Test Example 2 A grape plant (cultivar: Berry A) was planted in each pot and was sprayed with a sufficient volume of a dilution with a predetermined concentration of a wettable powder obtained according to Formulation Example 5, after the plant put out a fourth leaf. After air-drying of the liquid chemical, the surfaces of the leaves were inoculated with a suspension of spores (2 x 105 spores/ml) of grape downy mildew fungus (Plasmopara viticola) by spraying. The plant was grown at 24°C for 1 week, after which the infection rate (%) was investigated. The results are shown in Table 2. Agent tested Amount of agent applied (ppm) Infection rate (%) Compound (a) 10 30 Mancozeb 50 25 Compound (a) + Mancozeb 10 + 50 0 Test Example 3 Each of plastic pots was filled with sandy loam and sown with cucumber (Sagamihanjiro), followed by growing in a greenhouse for 14 days. A wettable powder of test agents prepared according to Formulation Example 11 was diluted to a predetermined concentration with water, and foliage application of the dilution was carried out so as to adhere the dilution sufficiently to the surfaces of leaves of the grown cucumber young seedling. After air-drying, gray mold fungus was inoculated on the surfaces of leaves of the young seedling, and the young seedling was grown in the dark at 10°C and a high humidity for 4 days, after which the infection rate (%) was investigated. The results are shown in Table 3. Agent tested Amount of agent applied (ppm) Infection rate (%) Compound (a) 10 30 Procymidone 10 25 Compound (a) + Procymidone 10 + 10 0 Test Example 4 Each of plastic pots was filled with sandy loam and sown with cucumber (Sagamihanjiro), followed by growing in a greenhouse for 14 days. Gray mold fungus was inoculated on the surfaces of leaves of the grown cucumber young seedling, and the young seedling was grown in the dark at 10°C and a high humidity for 2 days and then at a temperature of 23°C for 3 days. A wettable powder of test agents prepared according to Formulation Example 11 was diluted to a predetermined concentration with water, and foliage application of the dilution was carried out so as to adhere the dilution sufficiently to the surfaces of leaves of the cucumber young seedling. After the spraying, the young seedling was grown in the dark at 10°C and a high humidity for 3 days, and then the infection rate (%) was investigated. The results are shown in Table 4. Agent tested Amount of agent applied (ppm) Infection rate (%) Compound (a) 10 30 Procymidone 10 25 Compound (a) + Procymidone 10 + 10 0

Claims: A fungicidal composition characterized by containing as active ingredients synergistically effective amounts of: (a) methyl α-methoxyimino-2-[(2-methylphenoxy)methyl]phenylacetate; and (b) at least one ethylenebis(dithiocarbamate) type fungicidal compound selected from zinc salt (Zineb), manganese salt (Maneb), or a salt with zinc and manganese (Mancozeb), or at least one N-(3,5-dichlorophenyl)imide type fungicidal compound selected from N-(3,5-dichlorophenyl-1,2-dimethylcyclopropane-1,2-dicarboxyimide (Procymidone), 3-(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione (Vinclozolin) or 3-(3,5-dichlorophenyl)-N-(1-methylethyl)-2,4-dioxo-1-imidazolidinecarboxamide (Iprodione). A method for controlling plant diseases which uses a fungicidal composition set forth in claim 1.

Inventors: OGURI YUKIO, OGURI, YUKIO
Applicants: SUMITOMO CHEMICAL CO, SUMITOMO CHEMICAL COMPANY LIMITED
Application year: 1994
Main classification: A01N37
IPC codes: A01N43, A01N37